The present invention relates to a concentrated dampening solution suitable after dilution for printing with a lithographic printing plate obtained according to the silver salt diffusion transfer process.
Furthermore the present invention relates to a method for printing by using said dampening solution and a lithographic printing plate obtained according to the silver salt diffusion transfer process.
Lithographic printing is carried out by feeding both water and oleophilic colored ink to the printing plate surface to allow the image areas to receive preferentially the colored ink and the non-image areas preferentially water and then transferring the ink deposited on image areas onto a substrate such as paper for example. Therefore, in order to obtain a print of good quality, it is necessary that oleophilicity of the image areas and hydrophilicity of the non-image areas are both strong enough so that when water and ink are applied, the image areas may receive sufficient amount of ink while the non-image areas may completely repel the ink. For this purpose, various methods for rendering the non-image areas insensitive to oil have been studied according to the type of printing plate materials and the printing methods.
That is, hitherto, as lithographic printing plate materials, there are presensitized plates (PS plates) with a support of metals such as aluminum, plate materials obtained by electrophotographic process (such as electro fax), so called master papers comprising a paper as substrate coated with a pigment together with a binder and photographic printing plate materials using silver salts as disclosed in Japanese Patent Kokoku No. 48-30562. Plate making methods and printing methods using solutions to render the non-image areas insensitive to oil and dampening solutions suitable for each of these materials have been studied and developed.
Lithographic printing plates which utilize transfer silver images obtained by silver complex diffusion transfer process as ink receptive areas are disclosed in Japanese Patent Kokoku No. 48-30562 and Japanese Patent Kokai Nos. 53-21602, 54-103104 and 56-9750 and are well known.
The principles of the silver complex diffusion transfer reversal process, hereinafter called DTR-process, have been described e.g. in U.S. Pat. No. 2,352,014 and in the book xe2x80x9cPhotographic Silver Halide Diffusion Processesxe2x80x9d by Andrxc3xa9Rott and Edith Weydexe2x80x94The Focal Pressxe2x80x94London and New York, (1972).
In the DTR-process non-developed silver halide of an information-wise exposed photographic silver halide emulsion layer material is transformed with a so-called silver halide solvent into soluble silver complex compounds which are allowed to diffuse into an image-receiving element and are reduced therein with a developing agent, generally in the presence of physical development nuclei, to form a silver image having reversed image density values (xe2x80x9cDTR-imagexe2x80x9d) with respect to the black silver image obtained in the exposed areas of the photographic material.
A DTR-image bearing material can be used as a planographic printing plate wherein the DTR-silver image areas form the water-repellant ink-receptive areas on a water-receptive ink-repellant background. For example, typical lithographic printing plates are disclosed e.g. EP-A-423399 and EP-A-410500.
The DTR-image can be formed in the image-receiving layer of a sheet or web material which is a separate element with respect to the photographic silver halide emulsion material (a so-called two-sheet DTR-element) or in the image-receiving layer of a so-called single-support element, also called mono-sheet element, which contains at least one photographic silver halide emulsion layer integral with an image-receiving layer in water permeable relationship therewith. It is the latter mono-sheet version which is preferred for the preparation of offset printing plates by the DTR method.
According to the preferred embodiment of the mono-sheet DTR-offset printing plate, disclosed in e.g. U.S. Pat. No. 4,722,535 and GB-P-1,241,661, a flexible support e.g. of paper or of an organic resin is provided in the order given with a silver halide emulsion layer and a layer containing physical development nuclei serving as the image-receiving layer. After information-wise exposure and development the imaged element is used as a printing plate without the removal of the now-useless emulsion layers.
Said type of mono-sheet DTR offset printing plates is not compatible with other types of printing plates with regard to dampening solutions. In order that said mono-sheet DTR offset printing plates show no ink acceptance in the non-printing areas (no staining), use should be made of special dampening solutions containing a sizable amount of a transparent pigment usually colloidal siliciumoxide as disclosed e.g. in U.S. Pat. No. 3,829,319, U.S. Pat. No. 4,238,279 and EP-A 304.662.
For economical reasons (less packaging material, less storage space, a smaller volume to transport) practically all dampening solutions, including the above mentioned dampening solutions are sold in a concentrated form and only diluted at the moment they are used on the printing press.
Said dampening solutions should have a pH between 3 and 6. This requirement stems from the fact that otherwise said dampening solutions are not compatible with the usual lithographic inks. To maintain the required pH, said dampening solutions has to comprise a buffer because otherwise the pH will vary due to different causes e.g. the dilution with tap water, the contact with the usually alkaline printing paper etc.
However, the above mentioned concentrated dampening solutions show a lack of shelf life due to the presence of this transparent pigment in said solutions having typically a pH between 3 and 6. Indeed, the lithographic active transparent pigment, mostly colloidal silica is not stable at said pH but is only stable at an alkaline pH of around 9 to 10. Colloidal silica which is stable at a pH below 7 is not lithographic active.
Use of a dampening solution which is not stable results in a cloudy outlook of the undiluted as well as of the diluted dampening solution. Furthermore, this instability may cause a soiling of the dampening unit of the printing apparatus. Possibly, other parts of the press may also get soiled in due time. When a dampening circulation system is used, which delivers dampening solution to one or several presses, this system is also very prone to get soiled. This soiling of the dampening unit or the dampening circulation system results in the need for a more frequent cleaning of said units (a cumbersome and time-consuming operation). Apart from soiling said instability of said dampening solutions may even result in a possible staining in the non-image areas of the printed copies because less active transparent pigment is present in the dampening solution.
So there is a need for a concentrated dampening solution containing silica which is stable at a pH below 7 and so yielding a stable dampening solution but which silica is lithographic active.
It is an object of the present invention to provide a stable concentrated dampening solution having lithographic activity for printing with a lithographic printing plate obtained according to the DTR-process.
It is a further object of the present invention to provide a method for lithographic printing using the above mentioned concentrated dampening solution and a lithographic printing plate obtained according to the DTR-process.
Still further objects of the present invention will become clear from the description hereinafter.
According to the invention there is provided a concentrated dampening solution for use in a lithographic printing process having a pH between 3 and 6 and comprising a water-soluble organic solvent, a phosphate salt and a transparent pigment, characterized in that said transparent pigment is a modified silica in which the silica particles have a number average size of 0.003 to 0.100 xcexcm and in which the silica particles are coated with chemically combined atoms of an amphoteric metal which forms an insoluble silicate at a pH between 5 and 12, said metal atoms being chemically bound through oxygen atoms to silicon atoms in the surface of said particles. and the amount of said metal being such that: Gram atoms M/Gram atoms Si=A/1250 to A/250000 where M is the metal and A is the surface area of the particles of the silica sol expressed in m2/g.
According to the present invention there is further provided a method for lithographic printing comprising the following steps:
preparing a lithographic printing plate according to the silver salt diffusion transfer process by (1) image-wise exposing an imaging element comprising on a support a photosensitive layer comprising a silver halide emulsion and an image receiving layer containing physical development nuclei in water permeable relationship with said emulsion layer and (2) developing said imaging element in the presence of developing agent(s) and silver halide solvent(s) using an alkaline processing liquid.
mounting said lithographic printing plate to a lithographic printing press, and
printing while supplying to said lithographic printing plate a printing ink and a diluted dampening solution obtained from a concentrated dampening solution having a pH between 3 and 6 and comprising a water-soluble organic solvent, a phosphate salt and a transparent pigment, characterized in that said transparent pigment is a modified silica in which the silica particles have a number average size of 0.003 to 0.100 xcexcm and in which the silica particles are coated with chemically combined atoms of an amphoteric metal which forms an insoluble silicate at a pH between 5 and 12, said metal atoms being chemically bound through oxygen atoms to silicon atoms in the surface of said particles, and the amount of said metal being such that : Gram atoms M/Gram atoms Si=A/1250 to A/250000 where M is the metal and A is the surface area of the particles of the silica sol expressed in m2/g and that said concentrated dampening solution is used on the printing press in a 1:100 to 10:100 dilution.
According to the present invention it has been found that a stable concentrated dampening solution having a pH between 3 and 6 and comprising a water-soluble organic solvent, a phosphate salt and a transparent pigment has a lithographic activity and is thus suitable for printing with a lithographic printing plate obtained according to the silver salt diffusion transfer process when said transparent pigment is a modified silica in which the silica particles have a number average size of 0.003 to 0.100 xcexcm and in which the silica particles are coated with chemically combined atoms of an amphoteric metal which forms an insoluble silicate at a pH between 5 and 12, said metal atoms being chemically bound through oxygen atoms to silicon atoms in the surface of said particles, and the amount of said metal being such that:
Gram atoms M/Gram atoms Si=A/1250 to A/250000 where M is the metal and A is the surface area of the particles of the silica sol expressed in m2/g.
The preparation of said modified silica is disclosed in U.S. Pat. No. 2,892,797 which therefor is incorporated herein by reference. Any silica aquasol wherein the particle size of the silica lies between 0.003 and 0.100 xcexcm can be used in said preparation. Sols to be treated can be slightly alkaline, with a pH in the range 7 to 11.
The silica sol is surface reacted to form a coating in which the treating metal is combined with the surface of the silica particles in the sol. The metals which can be used are those which are amphoteric and which form an insoluble silicate at a pH between 5 and 12. Aluminum, tin, zinc and lead are preferred, aluminum being the most preferred of these. The metals can be added to the silica aquasol in the form of an alkali metalate such as sodium or potassium aluminate, stannate, zincate or plumbite. The amount of the metal treating agent added to the sol should be carefully controlled. Enough of the metal should be used to effect a desired treatment. Too much should not be used or else the sol will then contain the metal compound as an impurity or it may even form a precipitate in the system. It is believed that the metal coats and becomes chemically bound to the surface of the silica particles. When the metal is aluminum it substitutes for silicon in the silica lattice and, because of an increased negative charge on the surface of the particles, the sol becomes more stable. Similarly with other metals the particles become more negative.
The silica aquasol and the aqueous solution of the metalate can be brought together at practically any concentration and under practically any condition provided only that the pH does not vary locally so as to go outside the ranges already given. The temperature of the treatment will ordinarilly be the ambient temperature. It is preferred that the metal be brought together with the silica sol in the substantial absence of salts. The final product after it has been prepared can be adjusted as to pH in the range 5 to 12 by deionization or dialysis to remove excess ions or by adding acid such as hydrochloric acid or alkali such as sodium hydroxyde. The final product of said preparation is a silica sol the particles of which are coated with less than a molecular layer of the combined metal as described above. The product pH can range from about 5 to 12, but especially interesting sols are those which are stabilized in the range from 5 to 7.
Preferably the ratio of Gram atoms M/Gram atoms Si=A/25000 to A/62500 where M is the metal and A is the surface area of the particles of the silica sol expressed in m2/g.
Preferably the number average size of the modified silica particles range from 0.005 xcexcm to 0.05 xcexcm. Preferentially said concentrated dampening solution comprises said modified silica in an amount between 15 g/l and 30 g/l, more preferably between 2.5 g/l and 20 g/l.
Dampening solutions suitable for use in the present invention are aqueous solutions comprising water-soluble organic solvents. Examples of such water-soluble organic solvents include alcohols, polyhydric alcohols, ethers, polyglycols and esters.
Examples of the alcohols include n-butyl alcohol, n-amyl alcohol, n-hexyl alcohol, 2-methylpentanol-1, secondary hexyl alcohol, 2-ethylbutyl alcohol, secondary heptyl alcohol and heptanol-3,2-ethylhexyl alcohol.
Examples of the polyhydric alcohols include ethylene glycol, hexylene glycol, octylene glycol, diethylene glycol and glycerol. Examples of the ethers include ethylene glycol monoethyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol monoethyl ether and diethylene glycol mono-n-hexyl ether.
Examples of the esters include diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.
Examples of polyglycols include polyethyleneglycols having an average molecular weight of 400 to 2000, polypropylene glycols having an average molecular weight of 400 to 2000, and block copolymers of ethylene glycol and propylene glycol.
The dynamic surface tension of the dampening solution is lowered by adding said organic solvents. A dampening solution according to the invention has preferably a dynamic surface tension range from 25 to 50 dyne/cm at 15xc2x0 C. when measured at most 1*10xe2x88x921 second after a surface of said solution is formed on the surface of a printing plate with the NOW-INSTANT WILHELMY DYNAMIC SURFACE TENSION ACCESSORY manufactured by Cahn Co, U.S.A.
The dampening solutions used in the present invention may contain from about 0.05 to 30%, preferably from 0.1 to 25%, more preferably from 1 to 20% by weight of these water-soluble organic solvents.
According to the invention the dampening solutions have a pH comprised between 3 and 6, more preferably between 4 and 6. Therefore said concentrated dampening solution comprises a phosphate salt i.e. NaH2PO4 as a buffer. The amount of the phosphate salt, expressed as NaH2PO4 lies preferably between 4 and 30 g/l, more preferably between 6 and 25 g/l.
The dampening solution preferably comprises also, in order to further improve its stability citrate ions in a total concentration between 0.5 mmole and 25 mmole, more preferably between 1 mmole and 20 mmole, most preferably between 1.5 mmole and 15 mmole. The term xe2x80x9ctotal concentration of citrate anionsxe2x80x9d represents the sum of the concentrations of citric acid and its salts regardless of their ionic charge.
Surfactants can be added to the dampening solution to increase the emulsification ratio in ink. The contents of these surfactants should not be higher than 1% by weight, preferably 0.0001 to 0.3% by weight when foaming is taken into consideration.
The dampening solution used in the present invention may also comprise thickening agents. Examples of thickening agents which can be used in the present invention include water-soluble cellulose derivatives, alginate and derivatives, gum, water-soluble modifications of starch, and water-soluble high-molecular homopolymers and copolymers. These compounds may be used either alone or as a mixture of two or more of them.
The concentration varies depending on the type of the thickening agents, but is preferably about 0.00005 to 1% by weight based on the amount of the dampening solution composition.
In general, the dampening solution used in the present invention comprises a (combination of) preservative(s), so that the composition is effective for controlling various kinds of mold, bacteria and yeast.
In addition to the above-described components, the dampening solution of the present invention may contain chelate compounds preferably in an amount of 0.00001 to 0.3% by weight based on the amount of the dampening solution and corrosion inhibitors preferably in an amount of 0.000001 to 0.5% by weight.
The concentrated dampening solution as described above is diluted with sufficient tap water or well water prior to being applied on the plate. The concentrated dampening solution is used on the printing press in a 1:100 to 10:100 dilution, preferably in a 2:100 to 6:100 dilution.
The dampening solution can be used alone or in combination with water-soluble organic solvents e.g. isopropanol or substitutes therefore.
According to a preferred embodiment of the present invention a lithographic printing plate is obtained by means of the DTR-process using an imaging element comprising on a support in the order given a silver halide emulsion layer and a layer containing physical development nuclei in water permeable relationship with said emulsion layer.
Layers being in water permeable contact with each other are layers that are contiguous to each other or only separated from each other by (a) water permeable layer(s). The nature of a water permeable layer is such that it does not substantially inhibit or restrain the diffusion of water or of compounds contained in an aqueous solution e.g. developing agents or the complexed silver.
Supports suitable for use in accordance with the present invention may be opaque or transparent, e.g. a paper support or resin support. When a paper support is used preference is given to one coated at one or both sides with an Alpha-olefin polymer. It is also possible to use an organic resin support e.g. poly(ethylene terephthalate) film or poly-Alpha-olefin films. The thickness of such organic resin film is preferably comprised between 0.07 and 0.35 mm. These organic resin supports are preferably coated with a hydrophilic adhesion layer which can contain water insoluble particles such as silica or titanium dioxide. Metal supports e.g. aluminum may also be used in accordance with the present invention.
The image receiving layer containing physical development nuclei is preferably free of hydrophilic binder but may comprise amounts upto 80% by weight of the total weight of said layer of a hydrophilic colloid e.g. polyvinyl alcohol to improve the hydrophilicity of the surface. Preferred development nuclei for use in accordance with the present invention are sulphides of heavy metals e.g. sulphides of antimony, bismuth, cadmium, cobalt, lead, nickel, palladium, platinum, silver, and zinc. Especially suitable development nuclei in connection with the present invention are palladium sulphide nuclei. Other suitable development nuclei are salts such as e.g. selenides, polyselenides, polysulphides, mercaptans, and tin (II) halides. Heavy metals, preferably silver, gold, platinum, palladium, and mercury can be used in colloidal form.
The photosensitive layer used according to the present invention may be any layer comprising a hydrophilic colloid binder and at least one silver halide emulsion, at least one of the silver halide emulsions being photosensitive.
The photographic silver halide emulsion(s) used in accordance with the present invention can be prepared from soluble silver salts and soluble halides according to different methods as described e.g. by P. Glafkides in xe2x80x9cChimie et Physique Photographiquexe2x80x9d, Paul Montel, Paris (1967), by G. F. Duffin in xe2x80x9cPhotographic Emulsion Chemistryxe2x80x9d, The Focal Press, London (1966), and by V. L. Zelikman et al in xe2x80x9cMaking and Coating Photographic Emulsionxe2x80x9d, The Focal Press, London (1966).
The silver halide emulsion for use in connection with the present invention is a silver chlorobromide emulsion that may contain silver bromide in the range from 0.1 mole % to 40 mole % and that may contain upto 2 mole % of silver iodide. Preferably, the amount of silver bromide is between 1 mole % and 30 mole %. An emulsion comprising more than 5 mole % of silver bromide preferably belongs to the core/shell type well known to those skilled in the art in the sense that substantially all the bromide is concentrated in the core. This core contains preferably 10 to 40% of the total silver halide precipitated, while the shell consist preferably of 60 to 90% of the total silver precipitated. A particularly preferred silver halide emulsion of this type is described in U.S. Pat. No. 5,059,508.
The average size of the silver halide grains may range from 0.10 to 0.70 xcexcm , preferably from 0.25 to 0.45 xcexcm.
Preferably during the precipitation stage iridium and/or rhodium containing compounds or a mixture of both are added. The concentration of these added compounds ranges from 10xe2x88x928 to 10xe2x88x923 mole per mole of AgNO3, preferably between 10xe2x88x927 and 10xe2x88x925 mole per mole of AgNO3.
The emulsions can be chemically sensitized e.g. by adding sulphur-containing compounds during the chemical ripening stage e.g. allyl isothiocyanate, allyl thiourea, and sodium thiosulphate. Also reducing agents e.g. the tin compounds described in BE-P 493,464 and 568,687, and polyamines such as diethylene triamine or derivatives of aminomethane-sulphonic acid can be used as chemical sensitizers. Other suitable chemical sensitizers are noble metals and noble metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium. This method of chemical sensitization has been described in the article of R.KOSLOWSKY, Z. Wiss. Photogr. Photophys. Photochem. 46, 65-72 (1951).
Apart from negative-working silver halide emulsions that are preferred for their high photosensitivity, use can be made also of direct-positive silver halide emulsions that produce a positive silver image in the emulsion layer(s) and a negative image on the image-receiving layer.
Suitable direct positive silver halide emulsions for use in accordance with the present invention are silver halide emulsions that have been previously fogged or that mainly form an internal latent image.
The silver halide emulsions of the DTR-element can be spectrally sensitized according to the spectral emission of the exposure source for which the DTR element is designed.
Suitable sensitizing dyes for the visible spectral region include methine dyes such as those described by F. M. Hamer in xe2x80x9cThe Cyanine Dyes and Related Compoundsxe2x80x9d, 1964, John Wiley and Sons. Dyes that can be used for this purpose include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, homopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly valuable dyes are those belonging to the cyanine dyes, merocyanine dyes, complex merocyanine dyes.
In the case of a conventional light source, e.g. tungsten light, a green sensitizing dye is needed. In case of exposure by an argon ion laser a blue sensitizing dye is incorporated. In case of exposure by a red light emitting source, e.g. a LED or a HeNe laser a red sensitizing dye is used. In case of exposure by a semiconductor laser special spectral sensitizing dyes suited for the near infra-red are required. Suitable infra-red sensitizing dyes are disclosed in i.a. U.S. Pat. Nos. 2,095,854, 2,095,856, 2,955,939, 3,482,978, 3,552,974, 3,573,921, 3,582,344, 3,623,881 and 3,695,888.
A preferred blue sensitizing dye, green sensitizing dye, red sensitizing dye and infra-red sensitizing dye in connection with the present invention are described in EP-A 554,585.
To enhance the sensitivity in the red or near infra-red region use can be made of so-called supersensitizers in combination with red or infra-red sensitizing dyes. Suitable supersensitizers are described in Research Disclosure Vol 289, May 1988, item 28952. The spectral sensitizers can be added to the photographic emulsions in the form of an aqueous solution, a solution in an organic solvent or in the form of a dispersion.
The silver halide emulsions may contain the usual emulsion stabilizers. Suitable emulsion stabilizers are azaindenes, preferably tetra- or penta-azaindenes, especially those substituted with hydroxy or amino groups. Compounds of this kind have been described by BIRR in Z. Wiss. Photogr. Photophys. Photochem. 47, 2-27 (1952). Other suitable emulsion stabilizers are i.a. heterocyclic mercapto compounds.
The silver halide emulsions may contain pH controlling ingredients. Preferably the emulsion layer is coated at a pH value near the isoelectric point of the gelatin to improve the stability characteristics of the coated layer. Other ingredients such as antifogging agents, development accelerators, wetting agents, and hardening agents for gelatin may be present. The silver halide emulsion layer may comprise light-screening dyes that absorb scattering light and thus promote the image sharpness. Suitable light-absorbing dyes are described in i.a. U.S. Pat. No. 4,092,168, U.S. Pat. No. 4,311,787 and DE-P 2,453,217.
More details about the composition, preparation and coating of silver halide emulsions suitable for use in accordance with the present invention can be found in e.g. Product Licensing Index, Vol. 92, December 1971, publication 9232, p. 107-109.
In addition to the above described emulsion layer and image receiving layer other hydrophilic colloid layers in water permeable relationship with these layers may be present. For example it is especially advantageous to include a base-layer between the support and the photosensitive silver halide emulsion layer. In a preferred embodiment said base-layer serves as an antihalation layer. On the other hand, in order to gain sensitivity, light reflecting pigments, e.g. titaniumdioxide can be present. Further this layer can contain hardening agents, matting agents, e.g. silica particles, and wetting agents. At least part of these matting agents and/or light reflection pigments may also be present in the silver halide emulsion layer the most part however preferably being present in said base-layer. As a further alternative the light reflecting pigments may be present in a separate layer provided between the antihalation layer and the photosensitive silver halide emulsion layer.
In a preferred embodiment in connection with this photographic material a backing layer is provided at the non-light sensitive side of the support. This layer which can serve as anti-curl layer can contain i.a. matting agents e.g. silica particles, lubricants, antistatic agents, light absorbing dyes, opacifying agents, e.g. titanium oxide and the usual ingredients like hardeners and wetting agents. The backing layer can consist of one single layer or a double layer pack.
The hydrophilic layers usually contain gelatin as hydrophilic colloid binder. Mixtures of different gelatins with different viscosities can be used to adjust the Theological properties of the layer. Like the emulsion layer the other hydrophilic layers are coated preferably at a pH value near the isoelectric point of the gelatin. But instead of or together with gelatin, use can be made of one or more other natural and/or synthetic hydrophilic colloids, e.g. albumin, casein, zein, polyvinyl alcohol, alginic acids or salts thereof, cellulose derivatives such as carboxymethyl cellulose, modified gelatin, e.g. phthaloyl gelatin etc.
The hydrophilic layers of the photographic element, especially when the binder used is gelatin, can be hardened with appropriate hardening agents such as those of the vinylsulfone type e.g. methylenebis(sulfonylethylene), aldehydes e.g. formaldehyde, glyoxal, and glutaraldehyde, N-methylol compounds e.g. dimethylolurea and methyloldimethylhydantoin, active halogen compounds e.g. 2,4-dichloro-6-hydroxy-s-triazine, and mucohalogenic acids e.g. mucochloric acid and mucophenoxychloric acid. These hardeners can be used alone or in combination. The binders can also be hardened with fast-reacting hardeners such as carbamoylpyridinium salts of the type, described in U.S. Pat. No. 4,063,952.
Preferably used hardening agents are of the aldehyde type. The hardening agents can be used in wide concentration range but are preferably used in an amount of 4% to 7% of the hydrophilic colloid. Different amounts of hardener can be used in the different layers of the imaging element or the hardening of one layer may be adjusted by the diffusion of a hardener from another layer.
The imaging element used according to the present invention may further comprise various kinds of surface-active agents in the photographic emulsion layer or in at least one other hydrophilic colloid layer. Suitable surface-active agents include non-ionic agents, anionic agents comprising an acid group, ampholytic agents and cationic agents. Preferably compounds containing perfluorinated alkyl groups are used.
This photographic material suitable for use in the present invention may further comprise various other additives such as e.g. compounds improving the dimensional stability of the photographic element, UV-absorbers, spacing agents and plasticizers.
Suitable additives for improving the dimensional stability of the photographic element are e.g. dispersions of a water-soluble or hardly soluble synthetic polymer e.g. polymers of alkyl (meth)acrylates, alkoxy(meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters, acrylonitriles, olefins, and styrenes, or copolymers of the above with acrylic acids, methacrylic acids, alpha-beta-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulphoalkyl (meth)acrylates, and styrene sulphonic acids.
The imaging element according to the present invention may be imaged by means of a wide choice of cameras, existing on the market. Horizontal, vertical and darkroom type cameras and contact-exposure apparatus are available to suit any particular class of reprographic work. The imaging element can also be exposed in accordance with the present invention with the aid of i.a. laser recorders and cathode ray tubes.
Subsequently, said photographic material is developed with the aid of an aqueous alkaline solution in the presence of (a) developing agent(s) and (a) silver halide solvent(s).
The alkaline processing liquid used for developing the imaging element in accordance with the method of the present invention preferably contains a silver halide solvent. Preferably the silver halide solvent is used in an amount between 0.01% by weight and 10% by weight and more preferably between 0.05% by weight and 8% by weight. Suitable silver halide solvents for use in connection with the present invention are e.g. 2-mercaptobenzoic acid, cyclic imides, oxazolidones and thiosulfates. Silver halide solvents that are preferably used in connection with the present invention are thiocyanates and alkanolamines.
Alkanolamines that are suitable for use in connection with the present invention may be of the tertiary, secondary or primary type. Examples of alkanolamines that may be used in connection with the present invention correspond to the following formula: 
wherein X and Xxe2x80x2 independently represent hydrogen, a hydroxyl group or an amino group, l and m represent 0 or integers of 1 or more and n represents an integer of 1 or more. Preferably used alkanolamines are e.g. N-(2-aminoethyl)ethanolamine, diethanolamine, N-methylethanolamine, triethanolamine, N-ethyldiethanolamine, diisopropanolamine, ethanolamine, 4-aminobutanol, N,N-dimethylethanolamine, 3-aminopropanol, N,N-ethyl-2,2xe2x80x2-iminodiethanol etc. or mixtures thereof.
According to the present invention the alkanolamines are preferably present in the alkaline processing liquid. However part or all of the alkanolamine can be present in one or more layers of the imaging element.
A further suitable type of silver halide solvents are thioether compounds. Preferably used thioethers correspond to the following general formula:
Zxe2x80x94(R1xe2x80x94S)txe2x80x94R2xe2x80x94Sxe2x80x94R3xe2x80x94Y
wherein Z and Y each independently represents hydrogen, an alkyl group, an amino group, an ammonium group, a hydroxyl, a sulfo group, a carboxyl, an aminocarbonyl or an aminosulfonyl, R1, R2 and R3 each independently represents an alkylene that may be substituted and optionally contain an oxygen bridge and t represents an integer from 0 to 10. Examples of thioether compounds corresponding to the above formula are disclosed in e.g. U.S. Pat. No. 4,960,683 and EP-A 547,662, which therefor are incorporated herein by reference.
Still further suitable silver halide solvents are meso-ionic compounds. Preferred meso-ionic compounds for use in connection with the present invention are triazolium thiolates and more preferred 1,2,4-triazolium-3-thiolates.
According to a preferred embodiment of the present invention at least part and most preferably all of the meso-ionic compound is present in the alkaline processing liquid used for developing the image-wise exposed imaging element. Preferably the amount of meso-ionic compound in the alkaline processing liquid is between 0.1 mmol/l and 25 mmol/l and more preferably between 0.5 mmol/l and 15 mmol/l and most preferably between 1 mmol/l and 8 mmol/l.
However the meso-ionic compound may be incorporated in one or more layers comprised on the support of the imaging element. The meso-ionic compound is in that case preferably contained in the imaging element in a total amount between 0.1 and 10 mmol/m2, more preferably between 0.1 and 0.5 mmol/m2 and most preferably between 0.5 and 1.5 mmol/m2. More details are disclosed in EP-A-0,554,585.
The alkaline processing liquid used in accordance with the present invention preferably has a pH between 9 and 14 and more preferably between 10 and 13. Said pH may be established by an organic or inorganic alkaline substance or a combination thereof. Suitable inorganic alkaline substances are e.g. potassium or sodium hydroxide, carbonate, phosphate etc. Suitable organic alkaline substances are e.g. alkanolamines. In the latter case the alkanolamines will provide or help maintain the pH and serve as a silver halide complexing agent.
The alkaline processing liquid may also contain (a) developing agent(s). In this case the alkaline processing liquid is called a developer. On the other hand some or all of the developing agent(s) may be present in one or more layers of the photographic material or imaging element. When all of the developing agents are contained in the imaging element the alkaline processing liquid is called an activator or activating liquid.
Silver halide developing agents for use in accordance with the present invention are preferably of the p-dihydroxybenzene type, e.g. hydroquinone, methylhydroquinone or chlorohydroquinone, preferably in combination with an auxiliary developing agent being a 1-phenyl-3-pyrazolidone-type developing agent and/or p-monomethylaminophenol. Particularly useful auxiliary developing agents are the 1-phenyl-3-pyrazolidones. Even more preferred, particularly when they are incorporated into the photographic material are 1-phenyl-3-pyrazolidones of which the aqueous solubility is increased by a hydrophilic substituent such as e.g. hydroxy, amino, carboxylic acid group, sulphonic acid group etc. Examples of 1-phenyl-3-pyrazolidones substituted with one or more hydrophilic groups are e.g. 1-phenyl-4,4-dimethyl-2-hydroxy-3-pyrazolidone, 1-(4-carboxyphenyl)-4,4-dimethyl-3-pyrazolidone etc. However other developing agents can be used.
At least the auxiliary developing agents are preferably incorporated into the photographic material, preferably in the silver halide emulsion layer of the photographic material, in an amount of less than 150 mg/g of silver halide expressed as AgNO3, more preferably in an amount of less than 100 mg/g of silver halide expressed as AgNO3.
According to the present invention the alkaline processing liquid used for developing an imaging element as described above preferably also contains hydrophobizing agents for improving the hydrophobicity of the silver image obtained in the image receiving layer. The hydrophobizing agents used in connection with the present invention are compounds that are capable of reacting with silver or silver ions and that are hydrophobic i.e. insoluble in water or only slightly soluble in water. Generally these compounds contain a mercapto group or thiolate group and one or more hydrophobic substituents e.g. an alkyl group containing at least 3 carbon atoms. Preferred hydrophobizing agents are mercapto-1,3,4-thiadiazoles as described in DE-A 1,228,927 and in U.S. Pat. No. 4,563,410, 2-mercapto-1,3,4-oxadiazoles, 3-mercapto-1,2,4-triazoles and long chain (at least 5 carbon atoms) alkyl substituted mercaptotetrazoles. The hydrophobizing agents can be used alone or in combination with each other. Particularly preferred compounds correspond to one of the following formulas: 
wherein R5 represents hydrogen or an acyl group, R4 represents alkyl, aryl or aralkyl. Most preferably used compounds are compounds according to one of the above formulas wherein R4 represents an alkyl containing 3 to 16 C-atoms.
According to the present invention the hydrophobizing agents are contained in the alkaline processing liquid in an amount of at least 0.1 g/l, more preferably at least 0.2 g/l and most preferably at least 0.3 g/l. The maximum amount of hydrophobizing agents will be determined by the type of hydrophobizing agent, type and amount of silver halide solvents etc. Typically the concentration of hydrophobizing agent is preferably not more than 1.5 g/l and more preferably not more than 1 g/l.
The alkaline processing liquid preferably also contains a preserving agent having antioxidation activity, e.g. sulphite ions provided e.g. by sodium or potassium sulphite. For example, the aqueous alkaline solution comprises sodium sulphite in an amount ranging from 0.15 to 1.0 mol/l. Further may be present a thickening agent, e.g. hydroxyethylcellulose and carboxymethylcellulose, fog inhibiting agents, e.g. potassium bromide, potassium iodide and a benzotriazole which is known to improve the printing endurance, calcium-sequestering compounds, anti-sludge agents, and hardeners including latent hardeners. In accordance with the present invention it is furthermore preferred to use a spreading agent or surfactant in the alkaline processing liquid to assure equal spreading of the alkaline processing liquid over the surface of the photographic material. Such a surfactant should be stable at the pH of the alkaline processing liquid and should assure a fast-overall wetting of the surface of the photographic material. A surfactant suitable for such purpose is e.g. a fluor containing surfactant such as e.g. C7F15COONH4. It is furthermore advantageous to add glycerine to the alkaline processing liquid so as to prevent crystallization of dissolved components of said alkaline processing liquid.
Development acceleration can be accomplished by addition of various compounds to the alkaline processing liquid and/or one or more layers of the photographic element, preferably polyalkylene derivatives having a molecular weight of at least 400 such as those described in e.g. U.S. Pat. Nos. 3,038,805xe2x80x944,038,075xe2x80x944,292,400xe2x80x944,975,354.
Subsequent to the development in an alkaline processing liquid in accordance with the present invention the surface of the printing plate is preferably neutralized using a neutralization liquid.
A neutralization liquid generally has a pH between 5 and 8. The neutralization liquid preferably contains a buffer e.g. a phosphate buffer, a citrate buffer or mixture thereof. The neutralization solution can further contain bactericides, substances which influence the hydrophobic/hydrophilic balance of the printing plate obtained after processing of the DTR element, e.g. hydrophobizing agents as described above, silica and wetting agents, preferably compounds containing perfluorinated alkyl groups.
A lithographic plate is thus obtained.
According to another embodiment of the present invention a lithographic printing plate can be obtained by means of the DTR-process using an imaging element comprising in the order given a hydrophilic surface of a support, a layer of physical development nuclei and a silver halide emulsion layer.
Said hydrophilic surface of a support can be a hardened hydrophilic layer, containing a hydrophilic binder and a hardening agent coated on a flexible support.
Such hydrophilic binders are disclosed in e.g. EP-A 450,199, which therefor is incorporated herein by reference. Preferred hardened hydrophilic layers comprise partially modified dextrans or pullulan hardened with an aldehyde as disclosed in e.g. EP-A 514,990 which therefor is incorporated herein by reference. More preferred hydrophilic layers are layers of polyvinyl alcohol hardened with a tetraalkyl orthosilicate and preferably containing SiO2 and/or TiO2 wherein the weight ratio between said polyvinylalcohol and said tetraalkyl orthosilicate is between 0.5 and 5 as disclosed in e.g. GB-P 1,419,512, FR-P 2,300,354, U.S. Pat. No. 3,971,660, U.S. Pat. No. 4,284,705, EP-A 405,016 and EP-A 450,199 which therefor are incorporated herein by reference.
Flexible supports e.g. a paper support or a resin support are described above.
Said hydrophilic surface of a support may be a hydrophilic metallic support e.g. an aluminum foil.
The aluminum support of the imaging element for use in accordance with the present invention can be made of pure aluminum or of an aluminum alloy, the aluminum content of which is at least 95%. The thickness of the support usually ranges from about 0.13 to about 0.50 mm.
The preparation of aluminum or aluminum alloy foils for lithographic offset printing comprises the following steps graining, anodizing, and optionally sealing of the foil.
Graining and anodization of the foil are necessary to obtain a lithographic printing plate that allows to produce high-quality prints in accordance with the present invention. Sealing is not necessary but may still improve the printing results. Preferably the aluminum foil has a roughness with a CLA value between 0.2 and 1.5 xcexcm, an anodization layer with a thickness between 0.4 and 2.0 xcexcm and is sealed with an aqueous bicarbonate solution.
According to the present invention the roughening of the aluminum foil can be performed according to the methods well known in the prior art. The surface of the aluminum substrate can be roughened either by mechanical, chemical or electrochemical graining or by a combination of these to obtain a satisfactory adhesiveness of a silver halide emulsion layer to the aluminum support and to provide a good water retention property to the areas that will form the non-printing areas on the plate surface.
The electrochemical graining process is preferred because it can form a uniform surface roughness having a large average surface area with a very fine and even grain which is commonly desired when used for lithographic printing plates.
Electrochemical graining can be conducted in a hydrochloric and/or nitric acid containing electrolyte solution using an alternating or direct current. Other aqueous solutions that can be used in the electrochemical graining are e.g. acids like HCl, HNO3, H2SO2, H3PO4, that if desired, contain additionally one or more corrosion inhibitors such as Al(NO3)3, AlCl3, boric acid, chromic acid, sulfates, chlorides, nitrates, monoamines, diamines, aldehydes, phosphates, H2O2, etc. . . .
Electrochemical graining in connection with the present invention can be performed using single-phase and three-phase alternating current. The voltage applied to the aluminum plate is preferably 10-35 V. A current density of 3-150 Amp/dm2 is employed for 5-240 seconds. The temperature of the electrolytic graining solution may vary from 5-50xc2x0 C. Electrochemical graining is carried out preferably with an alternating current from 10 Hz to 300 Hz.
The roughening is preferably preceded by a degreasing treatment mainly for removing greasy substances from the surface of the aluminum foil.
Therefore the aluminum foil may be subjected to a degreasing treatment with a surfactant and/or an aqueous alkaline solution.
Preferably roughening is followed by a chemical etching step using an aqueous solution containing an acid. The chemical etching is preferably carried out at a temperature of at least 30xc2x0 C. more preferably at least 40xc2x0 C. and most preferably at least 50xc2x0 C.
Suitable acids for use in the aqueous etch solution are preferably inorganic acids and most preferably strong acids. The total amount of acid in the aqueous etch solution is preferably at least 150 g/l. The duration of chemical etching is preferably between 3 s and 5 min.
After roughening and optional chemical etching the aluminum foil is anodized which may be carried out as follows.
An electric current is passed through the grained aluminum foil immersed as an anode in a solution containing sulfuric acid, phosphoric acid, oxalic acid, chromic acid or organic acids such as sulfamic, benzosulfonic acid, etc. or mixtures thereof. An electrolyte concentration from 1 to 70% by weight can be used within a temperature range from 0-70xc2x0 C. The anodic current density may vary from 1-50 A/dm2 and a voltage within the range 1-100 V to obtain an anodized film weight of 1-8 g/m2 A12O3.H2O. The anodized aluminum foil may subsequently be rinsed with demineralized water within a temperature range of 10-80xc2x0 C.
After the anodizing step sealing may be applied to the anodic surface. Sealing of the pores of the aluminum oxide layer formed by anodization is a technique known to those skilled in the art of aluminum anodization. This technique has been described in e.g. the xe2x80x9cBelgisch-Nederlands tijdschrift voor Oppervlaktetechnieken van materialenxe2x80x9d, 24ste jaargang/januari 1980, under the title xe2x80x9cSealing-kwaliteit en sealing-controle van geanodiseerd Aluminumxe2x80x9d. Different types of sealing of the porous anodized aluminum surface exist.
Preferably, said sealing is performed by treating a grained and anodized aluminum support with an aqueous solution containing a bicarbonate as disclosed in EP-A 567178, which therefor is incorporated herein by reference.
Preferably each of the above described steps is separated by a rinsing step to avoid contamination of the liquid used in a particular step with that of the preceding step.
To promote the image sharpness and, as a consequence thereof, the sharpness of the final printed copy, the anodization layer may be coloured in the mass with an antihalation dye or pigment e.g. as described in JA-Pu-58-14,797.
As binder in the silver halide emulsion layer(s) in connection with the present invention a hydrophilic colloid may be used, usually a protein, preferably gelatin. Gelatin can, however, be replaced in part or integrally by synthetic, semi-synthetic, or natural polymers. Preferably the silver halide emulsion layer contains at least one gelatin species whereof a 10% by weight aqueous solution at 36xc2x0 C. and pH 6 has a viscosity lower than 20 mPas at a shearing rate of 1000 sxe2x88x921 combined with a gelatin of a higher viscosity. The weight ratio of said low viscosity gelatin versus the gelatin of a higher viscosity is preferably  greater than 0.5.
Preferably the gelatin layer(s) is(are) substantially unhardened. Substantially unhardened means that when such gelatin layer is coated on a subbed polyethylene terephtalate film base at a dry thickness of 1.2 g/m2, dried for 3 days at 57xc2x0 C. and 35% R.H. and dipped in water of 30xc2x0 C., said gelatin layer is dissolved for more than 95% by weight within 5 minutes.
The imaging element of the present embodiment may be imaged using a camera-exposure or a scanning exposure as described above followed by a development step in the presence of development agent(s) and silver halide solvent(s) according to the invention so that a silver image is formed in the physical development nuclei layer. Subsequently the silver halide emulsion layer and any other optional hydrophilic layers are removed by e.g. rinsing the imaged element with water, preferably between 30xc2x0 C. and 50xc2x0 C. so that the silver image is exposed.
To facilate the removal of the silver halide emulsion layer it is advantageous to provide a layer between the hydrophilic surface of a support and the silver halide emulsion layer comprising a hydrophilic non-proteinic film-forming polymer e.g. polyvinyl alcohol, polymer beads e.g. poly(meth)acrylate beads, mixtures thereof, particles of a water insoluble inorganic compound having a number average size not lower than 0.1 xcexcm or alkali insoluble non-polymeric organic compounds having a melting point of at least 50xc2x0 C. and a number average size between 0.1 xcexcm and 10 xcexcm. Such type of layers are disclosed in EP-A-483415, EP-A-410500, EP-A-94203779.7 and EP-A-95. . . .
Finally said exposed imaged surface of the hydrophilic support is treated with a finisher to enhance the water-receptivity of the non-image areas and to make the image areas oleophilic ink-receptive.
The lithographic composition often called finisher comprises at least one compound enhancing the ink-receptivity and/or lacquer-receptivity of the silver image and at least one compound that improves the ink-repelling characteristics of the hydrophilic surface.
Suitable ingredients for the finisher are e.g. organic compounds containing a mercapto group such as the hydrophobizing compounds referred to hereinbefore for the alkaline solution. Said (a) hydrophobizing agent(s) is(are) comprised in the finisher preferably in a total concentration between 0.1 g/l and 10 g/l, more preferably in a total concentration between 0.3 g/l and 3 g/l.
Additives improving the oleophilic ink-repellency of the hydrophilic surface areas are e.g. carbohydrates such as acid polysaccharides like gum arabic, carboxymethylcellulose, sodium alginate, propylene glycol ester of alginic acid, hydroxyethyl starch, dextrin, hydroxyethylcellulose, polyvinyl pyrrolidone. polystyrene sulphonic acid, polyvinyl alcohol and preferably polyglycols, being the reaction products of ethyleneoxide and/or propyleneoxide with water or an alcohol. Optionally, hygroscopic substances e.g. sorbitol, glycerol, tri(hydroxyethyl)ester of glycerol, and turkish red oil may be added.
A lithographic plate is thus obtained.
In accordance with the present invention in a following step the lithographic plate is mounted on a lithographic press and treated with a diluted dampening solution as described above and with a lithographic ink in order to print.
Any of the conventional lithographic inks can be used in the present invention. Examples of the lithographic inks include black ink, general process color ink, pantone color ink, magnetic ink, gold and silver ink, UV curable ink, ink for synthetic paper, fluoresent ink and metallic ink etc.
The dampening system suitable for use in the present invention is preferably an integrated system, whereby the dampening solution and the ink are brought into contact with each other before applying them to the lithographic plate e.g. by feeding the dampening solution to inked rollers. The dampening system used in the present invention may also be a conventional separated system, whereby the dampening solution is fed to the lithographic plate using fabric covered rollers independent of the inked rollers. Also hybrid dampening systems may be used in the present invention, whereby some dampening solution is brought into contact with the ink before applying the mixture to the lithographic plate and some dampening solution is fed directly to the lithographic plate using rubber rollers independent of the inked rollers.
As printing press any lithographic printing press can be used.
Printing can be effected on any ink-receptive element i.a. depending on the required printing effect. In general, paper is used but also cardboard can be used.